Methods for the Manufacture of Colorfast Masonry

ABSTRACT

The invention is directed to compositions and methods for the manufacture of pigmented solids structures for which can be used for construction and/or decoration. Manufacturing comprises fixing one or more pigments to an aggregate material such as crushed rock, stone or sand. The pigmented aggregate is incubated with urease or urease producing microorganisms, an amount of a nitrogen source such as urea, and an amount of calcium source such as calcium chloride forming calcite bridges between particles of aggregate. The resulting solid has a hardness and colorfastness for most any construction material. Using selected aggregate and pigment, the process also provides for the manufacture of simulated-stone materials such as clay or granite bricks or blocks, marble counter-tops, and more. The invention is also directed to composition containing microorganisms and pigment as kits that can be added to most any aggregate materials.

REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.15/455,689, filed Mar. 10, 2017, now U.S. Pat. No. 10,717,674, which isa continuation-in-part of U.S. application Ser. No. 15/066,692 filedMar. 10, 2016, which claims priority to U.S. Provisional Application No.62/200,288 filed Aug. 3, 2015, U.S. Provisional Application No.62/188,556 filed Jul. 3, 2015, and U.S. Provisional Application No.62/130,854 filed Mar. 10, 2015, and claims priority to U.S. ProvisionalApplication No. 62/358,937 filed Jul. 6, 2016, the entirety of each ofwhich is hereby specifically incorporated by reference.

BACKGROUND 1. Field of the Invention

The invention is directed to kits, compositions, tools and methods forthe manufacture of construction materials with artificial and/or addedcolor. More particularly, the invention is directed to compositions,materials and methods for the manufacture of bricks and masonry blockswith a variety of colors, color patterns and colors that simulatenatural materials such as bricks, cement and stone.

2. Description of the Background

Cement is manufactured from hydraulic calcium silicates containingcalcium sulfate with other components. This composition is heated tohigh temperature and mixed with limestone, shale and other naturallyoccurring materials that are generally white or gray. These cementsgenerally considered to be uncolored. The addition of pigments or dyesto uncolored cement creates a colored cement composition such asdescribed in U.S. Pat. No. 4,204,876 which discloses a pigmentcontaining thixotropic slurry that can be stored in drums for 6-12months by a cement contractor and used in a batching system. Also, U.S.Pat. Nos. 5,558,708 and 5,846,315 disclose methods, composition andsystem for preparing pigmented cement compositions employing an aqueouscomponent that contains a pigment and a dry powdered component. Othermethods for preparing colored or pigmented cement compositions aredescribed in U.S. Pat. Nos. 5,199,986, 3,667,976, and 4,946,505.

A product referred to as COLORQUARTZ is an aggregate that containsquartz particles ceramically coated by a process that permanently bondsinorganic pigments to the quartz particle. Particles are prepared byfiring with intense heating at temperatures of 315° C. (600° F.) orhigher. The particles are available in an S grade, which are sphericalshaped particles and a T grade which are trowable particles, and areabout 12-70 mesh or larger. The ceramically coated granules can be addedto cement compositions such as plasters or flooring compositions toprovide specks of color throughout the area or flooring, and do notprovide a uniform color to the cement composition.

Gray cement can be prepared by employing a naturally occurring graycalcium carbonate product as an inert filler. The naturally occurringgray calcium carbonate exhibits a very high sulfur content that mayadversely affects the final properties of the cured product, but theproduct is otherwise gray. Attempts at preparing colored cementcompositions have included crushing naturally occurring colored marble,such as a green marble, and using the crushed colored marble as theinert filler in the cement composition. With this process, colors arelimited and inhomogeneously dispersed and, accordingly, additionalpigment is usually required with the problems and disadvantagesassociated therewith.

A disadvantage of preparing colored cement is that the pigment used toprepare the colored cement is typically dispersed throughout the fluidcomposition rather than being fixed to any of the solids in thecomposition and, thus, dispersion of the pigment leads to leaching whilethe cement is hydrating. In addition, the dispersion of pigments incement compositions often results in color differences between batchesdue to variations in starting materials the fact that pigments tend tofloat to the surface.

SUMMARY OF THE INVENTION

The present invention overcomes problems and disadvantages associatedwith current strategies and designs and provides new tools, compositionsand methods for the manufacture of colored solid structures such asbricks and masonry.

One embodiment of the invention is directed to methods for producingsolid structures such as masonry containing any one or more of a varietyof pigments and pigment combinations. Preferably, the method of theinvention comprises combining a coloring agent (e.g., a pigment) with anaggregate material. Preferably the coloring agent is red, blue, green,yellow and/or combinations or varying hues and/or shades thereof.Compositions may also contain an identifying agent or a detectablemarker such as a microscopic tag, a color, an enzyme or anothersubstance. Coloring agents can be added to most any aggregate material.Preferably the aggregate comprises organic or inorganic material suchas, for example, sand, rock, glass (e.g. Poraver), wood, paper, metal,plastic, polymers, minerals, recycled materials, or combinationsthereof. Pigment may be added to aggregate as a liquid, gel, paste, ordry powder. Aggregate is preferably in the form of beads, grains, rods,strands, fibers, flakes, crystals, pulverized or crushed materials, orcombinations thereof. Pigment is adhered to aggregate with a hydrationof 5% or less, preferably 2% or less, and preferably 1% or less, and byagitation such as by mixing. Optionally, a small amount of liquid suchmay be added followed by another period of agitation, preferably tohomogeneity. Once aggregate is colored, the colored aggregate isprocessed in accordance with procedures for the manufacture of calcitebonding between particles. The resulting solid structure contains thedesired color or color combination, which may be uniform throughout thestructure or of a design.

Another embodiment of the invention is directed to compositionscomprising solid masonry containing any one or more of a variety ofpigments and pigment combinations. Preferably the solid forms areblocks, boards, bricks, pavers, panels, tiles, or veneer, and themixture further contains fibers or nanofibers that are, for example,fibers or nanofibers of wood, glass, plastic, metal or a polymer.Preferred fibers include, for example, polypropylene, HDPE, carbonfibers including high-strength carbon fibers, rayon, and biodegradablefibers such polymers of poly lactic acid, fibers of cellulose, minerals,chitin, and other plant materials. Solid structures may simulate naturalmaterials such as, for example, slate, brick, marble, and othernaturally occurring materials and especially construction materials. Thepigmented solid structures made by the method of the invention do notleach pigment upon exposure to environmental conditions for a period oftime preferably wherein the environmental conditions comprise one ormore of rain, snow, visible light, rain, and temperature variations.Preferably the period of time is greater than ten years, and morepreferably for the useful life of the masonry.

Another embodiment of the invention is directed to kits formanufacturing solid masonry forms with added color. Kits preferablycomprise a composition comprising urease-producing spores or cells and apigment, optionally an activating agent, and a nutrient media. Cells orcell spores may be encapsulated or coated with nutrient media such as,for example, proteins or polysaccharides, or polymers such as polylactic acid which is water soluble. Preferably the nutrient mediafurther contains additional urease producing cells, supporting cells, orspores.

Another embodiment of the invention is directed to methods formanufacture of solid forms comprising: mixing different sized or shapedaggregate material with pigment wherein, preferably, the pigmentedaggregate material is largely composed of particulates of less than 5 mmin diameter. After mixing a small amount of a liquid, preferably wateror another aqueous solution, is added and thoroughly mixed with thepigmented aggregate. The pigmented aggregate is processed in accordancewith MICP to form calcite which, preferably, may be apportioned intomultiple form works or extruded.

Other embodiments and advantages of the invention are set forth in partin the description, which follows, and in part, may be obvious from thisdescription, or may be learned from the practice of the invention.

DESCRIPTION OF THE INVENTION

Traditional construction materials such as bricks and concrete requireenormous amounts of energy during the manufacturing process. The colorsof bricks and concrete most often reflect the color of the beginningaggregate which are often, for example, clay or a stone. Bricks andconcrete can be artificially colored, but when colorants are addedduring manufacturing, the pigments remain in the liquid portion betweenparticles of the aggregate. As the aggregate particles are compressed,such as with clay bricks, the spaces between particles diminish and theadded color is virtually eliminated. With concrete, added color does notadhere to the particles and again, the natural color of the aggregateparticles dominates forming a mosaic or colored cement and stone.Consequently, color changes of bricks and cement typically involvepainting of the exposed surfaces. Painting requires repeatedapplications after periods of time with the periods determined by thequality of the paint and the conditions to which structures are exposed.

It is well established that an alternative to traditional brick makingis available that consumes significant less energy and utilizes nearlyany loose aggregate material as the base. This alternative employsnatural microorganisms to manufacture bricks and/or masonry and can usemost any base aggregate material. The process involves incubation ofaggregate with enzymes that catalyze the precipitation of calcite.Traditionally, the solid forms created retain the color of the baseaggregate or, like traditional bricks and cement, can be painted. It hassurprisingly discovered that solid structures that are formed frommicrobial induced calcite precipitation (MICP) can be formed with mostany color or color combination. In contrast to colored cement, accordingto the invention, pigment colors the aggregate surfaces and, thus, isvisible throughout the finished solid and on all sides containingexposed aggregate. Solid structures thereby created can be uniform incolor throughout, or colored in patterns or designs as desired.

An advantage of this process is that pigment is fixed to the surfaces ofaggregate particles without the need for extreme heat or pressure andwithout the use of harsh chemicals. The process of the invention ispreferably performed at ambient temperatures and pressures, and with noadded chemicals as are typically used to create covalent bonds betweenpigment and aggregate surfaces. Heating of aggregate and pigment, ifneeded, is generally optional and typically utilized only with selectedpigment chemical types. Another advantage of the invention is that thecalcite, which forms between aggregate particles, is largely transparentand, as such, reflects the color of the pigmented aggregate particlesthereby enhancing color intensity. Precipitated calcite further securesadherence of the pigment to the aggregate particles and also that thecalcite crystals align the wavelength of reflected light.

Another advantage of the invention is that solid forms composed of thecolored aggregate according to the invention retains a strongcolorfastness. Colorfastness is at least as strong as painting and inmost instances, the colorfastness of the solid is greater to and/or moreresilient than as otherwise achieved from surface painting.Colorfastness was determined after exposure to simulated enhancedweathering conditions including exposure to sun, rain, heat, cold, salt,acid, base, and combinations thereof. As determined by visual analysis,there was no significant change or fading of color. Colorfastness wasalso determined by analyzing the pigment content of aqueous solutionsafter washing of the artificially colored solid structures includingwashing under pressure. Pigment was undetectable in effluent of the washsolutions. Colorfastness of solid forms manufactured according to themethod of the invention is at least as colorfast as painted or stainedbricks, cinder blocks or other construction materials. Preferably thecolorfastness is retained for the useful life of the solid, which ispreferably 10 years or more, 15 years of more, 20 years or more, 30years or more, 50 years or more. As the pigment is a part of the masonryand believed to be affixed and effectively sealed with calcite bonds toaggregate surfaces, repeated painting is avoided and washing, if andwhen needed, does not alter colorfastness of the solid structure.

Another advantage of the invention is that solid structures can bemanufactured with a desired hardness, load bearing capability andresistance to fracture. Load bearing was determined by standardprocedures to measure the capability of the solid form to withstandweight and load without fracturing. By increasing the period of time forcalcite formation and/or the number of cycles of calcite formation,hardness can be increased as desired. Hardness, load bearing capacityand resistance to fracture can be achieved that are equal to and greaterthan the same measure for comparable construction material such asbricks, pavers, cinder blocks and the like.

It has also been surprisingly discovered that solid structures that areformed from microbial induced calcite precipitation (MICP) according tothe invention can be colored in a manner that simulates most any type ofstone including, for example, bricks, slate, concrete, bluestone,granite, marble, and combinations thereof. As the solid structures ofthe invention can be manufactured with a variety of aggregate types andwith various colors and color combination, those skilled in art canselect aggregate type and colors or color combinations that simulatemost any other material. In addition, this process allows for thecreation of an unlimited number of designs and non-natural patterns asone may wish including, but not limited to combinations of differentaggregate materials, combinations of different colors and combinationsof designs and patterns of aggregates and/or colors.

One embodiment of the invention is directed to methods of producingartificially colored solid structures. In this method an aggregatematerial is selected and combined with a pigment. Preferably theaggregate material comprises most any type of natural rock or stone,glass, fiberglass, wood, biomass, paper, metal, plastic, polymers,rubber, imitation rubber, vinyl, minerals, imitations of rock or stone,recycled materials such as, for example, recycled brick, concrete,stone, mine tailings and mining residues, scrubber wastes, and/orcombinations thereof. Aggregate can be of any size including mixtures ofsizes provided such aggregate is smaller in size than the resultingstructure. Preferably aggregate materials are particles of aggregate of10 mm or less, 5 mm or less, 1 mm or less, 0.5 mm or less, orcombinations thereof. Mesh sizes can be as desired including but notlimited to very fine particles (any number between and including 32-300standard mesh), fine particles (any number between and including 10-32standard mesh), medium particles (less than 10 standard mesh includingall mesh numbers therein), and coarse particles (particles greater thanor equal to 2 mm), and combinations thereof. Particle can be most anyshape including, for example, round or rounded, oval, spherical (Sgrade), square, rectangular, hedral, fiber, lath, angular, elongated,needle-like, acicular, flat, flaky, cylindrical, spongy, cubic, cubicaland combinations and variations thereof. If desired or necessary,aggregate particles can be roughened to create cracks in and crevices onparticle surfaces. Roughening can be performed by mixing particlestogether in a mixer or blender with sufficient force to create cracks inand crevices on particle surfaces, by adding ball bearings or anothersubstance to the aggregate particles with a hardness equal to or greaterthan the particles themselves, by passing particles over a rougheningagent such as, for example, sand, steel, or industrial diamonds, oranother roughening agent known to those skilled in the art orcombinations thereof.

A pigment is any material that changes the color of reflected ortransmitted light as the result of wavelength-selective absorption.According to the invention, the term pigment also includes materialsthat create fluorescence, phosphorescence, luminescence or another formor artificial color in which the resulting solid structure emitsselected light waves. Pigments that can be utilized include organicpigments, inorganic pigments, synthetic pigments, metallic pigments,lake pigments, biological pigments, pigments obtained or derived fromplants, animals and/or bacteria, natural pigments, mineral pigments, andcombinations thereof. A listing of selected pigments (all commerciallyavailable) useful for the invention is provided in Table 1.

TABLE 1 Purple pigments Aluminum pigments Ultramarine violet: (PV15)Silicate of sodium and aluminum containing sulfur. Copper pigments: HanPurple: BaCuSi₂O₆. Cobalt pigments: Cobalt Violet: (PV14) cobaltousorthophosphate. Manganese pigments: Manganese violet: NH₄MnP₂O₇ (PV16)Manganic ammonium pyrophosphate Phthalo pigments: Phthalocyanine Bluepigments Aluminum pigments: Ultramarine (PB29): a complex naturallyoccurring pigment of sulfur- containing sodio-silicate(Na₈₋₁₀Al₆Si₆O₂₄S₂₋₄); lapis; lazule Cobalt pigments: Cobalt Blue (PB28)and Cerulean Blue (PB35): cobalt(II) stannate Copper pigments: EgyptianBlue: a synthetic pigment of calcium copper silicate (CaCuSi₄O₁₀). HanBlue: BaCuSi₄O₁₀ Iron pigments: Prussian Blue (PB27): a syntheticpigment of ferric hexacyanoferrate (Fe₇(CN)₁₈). The dye Marking blue ismade by mixing Prussian Blue and alcohol. Manganese pigments: YInMnBlue: a synthetic pigment (YIn_(1−x)Mn_(x)O₃) Green pigments Cadmiumpigments: Cadmium Green: a light green pigment consisting of a mixtureof Cadmium Yellow (CdS) and Viridian (Cr₂O₃) Chromium pigments: Chromegreen (PG17): chromic oxide (Cr₂O₃) Viridian (PG18): a dark greenpigment of hydrated chromic oxide (Cr₂O₃•H₂O) Copper pigments: Azurite:cupric carbonate hydroxide (Cu₃(CO₃)₂(OH)₂) Malachite: cupric carbonatehydroxide (Cu₂CO₃(OH)₂) Paris Green: cupric acetoarsenite(Cu(C₂H₃O₂)₂•3Cu(AsO₂)₂) Scheele's Green (also called Schloss Green):cupric arsenite (CuHAsO₃) Verdigris: various poorly soluble coppersalts, notably cupric acetate (Cu(CH₃CO₂)₂) and malachite (Cu₂CO₃(OH)₂)Yellow pigments Arsenic pigments: Orpiment natural monoclinic arsenicsulfide (As₂S₃), Cadmium pigments: Cadmium Yellow (PY37): cadmiumsulfide (CdS) Chromium pigments: Chrome Yellow (PY34): natural pigmentof plumbous chromate (PbCrO₄). Cobalt pigments: Aureolin(also calledCobalt Yellow) (PY40): Potassium cobaltinitrite (Na₃Co(NO₂)₆). IronPigments: Yellow Ochre (PY43): a naturally occurring clay ofmonohydrated ferric oxide (Fe₂O₃•H₂O) Lead pigments: Naples Yellow(PY41); lead-tin-yellow Titanium pigments: Titanium Yellow (PY53) TinPigments: Mosaic gold: stannic sulfide (SnS₂) Orange pigments Cadmiumpigments: Cadmium Orange (PO20): an intermediate between cadmium red andcadmium yellow: cadmium sulfoselenide. Chromium pigments: Chrome Orange:a naturally occurring pigment mixture composed of lead (II) chromate andlead (II) oxide. (PbCrO₄ + PbO) Red pigments Cadmium pigments: CadmiumRed (PR108): cadmium selenide (CdSe) Iron oxide pigments: Sanguine,Caput Mortuum, Venetian Red, Oxide Red (PR102) Red Ochre (PR102):anhydrous Fe₂O₃ Burnt Sienna (PBr7): a pigment produced by heating RawSienna. Lead pigments: Red Lead: lead tetroxide, Pb₃O₄ Mercury pigments:Vermilion (PR106): Synthetic and natural pigment: Occurs naturally inmineral cinnabar. Mercuric sulfide (HgS) Brown pigments Clay earthpigments (naturally formed iron oxides) Raw Umber (PBr7): a natural claypigment consisting of iron oxide, manganese oxide and aluminum oxide:Fe₂O₃ + MnO₂ + nH₂O + Si + AlO₃. When calcined (heated) it is referredto as Burnt Umber and has more intense colors. Raw Sienna (PBr7): anaturally occurring yellow-brown pigment from limonite clay. Blackpigments Carbon pigments: Carbon Black (PBk7) Ivory Black (PBk9) VineBlack (PBk8) Lamp Black (PBk6) Iron Pigments: Iron black (PBk11) (C.I.No.77499): Fe₃O₄ Titanium pigments: Titanium Black ( ): Titanium(III)oxide (Ti₂O₃) White pigments Antimony pigments: Antimony White: StibousOxide (Sb₂O₃) Barium pigments: Barium sulfate (PW5): (BaSO₂) Leadpigments: Cremnitz White (PW1): basic Plumbous Carbonate((PbCO₃)₂•Pb(OH)₂) Titanium pigments: Titanium White (PW6): TitanicOxide (TiO₂) Zinc pigments: Zinc White (PW4): Zinc Oxide (ZnO) Otherpigments Fluorescent pigments Luminescent pigments Phosphorescentpigments Organic pigments Biologically-Derived pigments

Pigments may be provided dry, such as in powder form, in a gel, as apaste, or suspended in solution (e.g., polar or non-polar, aqueous ornon-aqueous). The amount of pigment added to the aggregate is from 1 mgto 10 g (dry weight) per kg of aggregate (dry weight), preferably from10 mg to 1 g (dry weight) per kg of aggregate (dry weight), and alsopreferably from 10 mg to 100 mg (dry weight) per kg of aggregate (dryweight). The amount of pigment added is dependent on the type ofaggregate, the form of aggregate (e.g., particle shape and size), thepigment selected, and also the desired color intensity of the finalproduct. Preferably, pigment is thoroughly mixed to homogeneity with theaggregate materials selected prior to the formation of calcite. Alsopreferably the pigment plus aggregate mixture has a fluid content of 5%by weight or less, more preferably 4% by weight or less, more preferably3% by weight or less, more preferably 2% by weight or less, morepreferably 1% by weight or less, and more preferably 0.5% by weight orless. Fluid is preferably water, steam or an aqueous liquid, but,depending on the pigment selected, may be a polar or non-polar solventsuch as benzene, dimethylsulfoxide (DMSO), an alcohol (e.g., methanol,ethanol, butanol, isopropyl) or combination thereof. Mixing ispreferably non-violent so as to minimize collisions between particles ofa force that would prevent adherence of pigment, but sufficientlythorough so that pigment is able to adhere to particle crevices andsurfaces as desired. Typical mixers include static mixers, rotatingdrums, tumblers, blenders, vessels containing rotating paddles orsticks, professional mixers, hand mixers, stirring apparatuses, electricmixers and the like. Mixing is preferably performed to achievehomogeneity so that an even layer of pigment exists over all or mostparticles.

Once pigment has been adhered to aggregate particles, optionally a smallamount of fluid, preferably water, is added to the mixture and themixture is once again thoroughly mixed preferably to homogeneity. Theamount of fluid added is preferably 5% by weight or less, morepreferably 3% by weight or less, more preferably 2% by weight or less,more preferably 1% by weight or less, and more preferably 0.5% by weightor less. The fluid plus pigmented aggregate mixture is preferably mixedusing the same apparatus as was used to mix pigment and aggregate. Oncethe fluid, and pigmented aggregate is thoroughly mixed, the aggregate isprocessed to a solid structure using enzymes as disclosed and describedin U.S. Pat. Nos. 8,728,365; 8,951,786 and 9,199,880 (all of which arespecifically and entirely incorporated by reference).

Briefly, a urea source, a calcium source and an enzyme source and/oroptionally the nutrient content when using urease-producing cells (e.g.,spores, bacterial cells, etc.) are added to the aggregate and incubatedfor a period of time to allow for the formation of calcite bonds betweenparticles. The amount of calcite formed between particles of aggregatecan be increased or decreased to create a desired level of hardness tothe structure. Variations can be achieved by varying the amounts ofcalcium, urea, enzyme and/or nutrients, and/or varying the time ofincubation or numbers of incubation cycles. Typically, urease-producingcells are aerobic and include, for example, Sporosarcina pasteurii,Sporosarcina ureae, Proteus vulgaris, Bacillus sphaericus, Myxococcusxanthus, Proteus mirabilis, Helicobacter pylori and other strains,serotypes, variations, mutations and CRISPR modifications (clusteredregularly interspaced short palindromic repeats). Cells produce theenzyme urease which, in the presence of calcium and nitrogen sources,forms calcite crystals under a process generally referred to asmicrobial induced calcite precipitation (MICP), which can be performedwith the activated cells or purified enzyme. When using spores, anactivating agent can be added to stimulate conversion of spores toactive cells. Typical activating agents include, for example, cellularnutrients such as amino acids, saccharides and polysaccharides.

The enzymes and/or the enzyme-producing cells or spores are dispersed ina composition containing the pigmented aggregate, urea, and calciumchloride. The composition may include or be combined with a supportmaterial which may be organic or inorganic and is preferably a solid orsemi-solid and preferably contains holes or perforations and/or isotherwise porous. Organic support material includes, for example,biomass such as, preferably, moss, hay, straw, grass, sticks, leaves,algae, dirt, dust, particulate material, refuse and combinationsthereof. Fibrous materials include sheets or tarps of burlap, paper,wood, cotton, or another natural fiber. Non-natural and manufacturedmaterials may also be used such as, for example, sheets of plastic,glass, fiberglass, vinyl, rubber, steel, iron or combinations thereof.To the solid support optionally may be applied otherwise may beintroduced other cells would be useful to support the grown of theurease-producing cells or enhance the chemical processes involved andnot otherwise interfere with the MICP process. Cells can be proliferateddirectly on the support material and, at a desired density or growthstage, the organic material evenly dispersed and/or thoroughly mixedinto an aggregate material for manufacture of construction tools andproducts. Inorganic materials that can be used include, for example,rock, sand, glass, wood, paper, metal, plastic, polymers, and minerals,any of which can be crushed or used whole or combinations thereof withan aggregate material catalyzing the production of ammonia and carbondioxide, increasing the pH level of the composition. The rise in pHforms a mineral precipitate combining calcium with carbon dioxide. Thecells or other particles act as nucleation sites, attracting mineralions from the calcium to the particle surfaces forming calcium carbonatecrystals such as calcite crystals or other calcium carbonate polymorphs.The mineral growth fills gaps between the particles of aggregate,bio-cementing or bonding aggregate particles forming a solid. Thismanufacturing method through induced cementation exhibits low embodiedenergy, and can occur at ambient pressure, and in a range oftemperatures from at least minus 20° C. to above 80° C. Preferably, thetemperature range is below 30° C., below 40° C., below 50° C., below 60°C., or below 70° C. The ambient temperatures and conditions as well asthe content of available aggregates can determine whether pure enzyme,lyophilized enzyme, spores, or live cells are utilized as the startingcomponents. Living cells can be used in temperatures where mild weatherconditions exist, whereas pure enzymes can be advantageous at moreextreme conditions of cold or heat. Spores are used when immediatecalcification is not required and the spores are provided sufficienttime to germinate and express enzyme.

Mixtures of colored aggregate, microbes and/or enzymes, urea, calciumand nutrients are incubated for one or more periods of time. Preferablyan incubation is for one or more hours, two or more hours, three or morehours, four or more hours, five or more hours, six or more hours, sevenor more hours, eight or more hours, nine of more hours, ten or morehours, eleven of more hours, twelve or more hours, or longer. The lengthof time of an incubation is largely determined by the size of the solidstructure being formed, temperature, the amount of nutrients providedand also the amount of substrate provided. Accordingly, incubation timescan be increased or decreased as desired by varying one or more of theseparameters.

The resulting solid structures exhibit a hardness and physicalproperties suitable for use in the construction of structures and whosehardness can be predetermined or preselected as desired. Hardness of thesolids formed according to the invention can be at least as hard as orgreater than natural brick, natural cement and any variations thereof.Solids manufactured according to the invention can be structural withsupporting necessary hardness requirements and/or be decorative.

Another embodiment of the invention is directed to the artificiallycolored solid structures manufactured according to the methods of theinvention. Solid structures can be nearly any color or color combinationas desired. As such, another embodiment of such structures and solidsthat simulate the appearance of other solids such as, for example,stone, slate, marble, brick, granite, solid construction materials,solid decorative materials, and combinations thereof. Solid structuresare formed by the MICP process according to the invention, but usingselected aggregate, aggregate particles sizes, and one or more pigments.The aggregate and pigments are selected and combined as described hereinprior to the MICP process. By selecting aggregate with a fine particlesize and gray, blue and black pigments, a simulated slate product can beformed. Fine particles and a variety of different colors and coloredcombinations of aggregate can be used to create simulated slate.Simulated bricks are manufactured using coarse aggregate which has beenpigmented with iron oxide. Pigment variations as found in natural brickcan be created by sprinkling a variety of black aggregate into the ironoxide-dyed aggregate prior to the MICP process. Surface texturing cangave the appearance of a different substance such as, for example,grinding a surface smooth and with pigment variations such as veiningcan provide the appearance of marble. Etching surfaces can provide anappearance of shale. Variations of aggregate type coupled with dots orsparkles of color can provide the appearance of granite. Any number ofshapes and textures can be created for decorative purposes as well.

Support materials and/or aggregate material may contain additionalcomponents that provide an advantage to the construction materials. Forexample, chemicals and/or additional cell (e.g., bacteria, yeast,eukaryotic cell, algae, and recombinant variations thereof), can beincluded that produce enzymes and/or other chemicals useful in breakingdown stains in and/or acquired by the final product. Stains includestains from air pollution, soot, mold or animal waste products.Alternatively, the chemical or enzymes may impart color, texture or adesired function or appearance to the final product.

Another embodiment of the invention is directed to kits formanufacturing artificially colored solid forms comprising one or moreof: colored aggregate materials of the invention or a composition forcoloring aggregate containing one or more pigments, a compositioncontaining nutrients for proliferation of the ureases-producing cellsand/or germination of the cell spores; a composition containing agentsfor stimulation of spores to a vegetative state and/or ureaseproduction; a plurality of sets of formworks wherein each set enclosesthe shape of at least one solid form and contains one or more porouspanels; and a third composition comprising a calcium source (e.g.,CaCl₂), a nitrogen source (e.g., urea) or both a calcium source and anitrogen source. Preferably the kit is for the creation of solid formssuch as, for example, rectangular, square, rounded, oval or an irregularshape. Preferred solid forms include but are not limited to blocks,boards, bricks, pavers, panels, tiles, counter tops, or veneer.Preferably kits of the invention are for the manufacture of blocks suchas, for example, concrete masonry, cinder blocks, foundation blocks,breeze blocks, hollow blocks, solid blocks, besser blocks, clinkerblocks, high or low density blocks, or aerated blocks. Nutrientcompositions of the invention may contain nutrient media to maintainand/or allow the cells to flourish and proliferate. The various types ofnutrient media for cells, and in particular, bacterial cells of theinvention are known and commercially available and include at leastminimal media (or transport media) typically used for transport tomaintain viability without propagation, and yeast extract, molasses, andcorn steep liquor, typically used for growth and propagation. Preferablythe nutrients and/or the agents to stimulate vegetative propagationinclude one or more of amino acids, proteins, polysaccharides, fattyacids, vitamins and minerals. Preferably form works comprise wood,plastic, composite materials, gel, foam, powder, or another materialthat maintains separation of aggregate material into forms, whereinnutrients can be provided and metabolic waste materials drained away.

Another embodiment of the invention is directed to methods formanufacture of solid forms comprising: mixing the composition of theinvention with an artificially colored aggregate material and water toform a mixture, wherein the aggregate material is largely composed ofparticulates of less than 5 mm in diameter (e.g. less than or about 4mm, less than or about 3 mm, less than or about 2 mm, or less than orabout 1 mm); apportioning the mixture into multiple form works whereineach form work contains at least one porous panel; adding a secondcomposition to the mixture, wherein the second composition containsnutrients that promote proliferation of the urease-producing cells;adding a third composition to the mixture, wherein the third compositionis a liquid, powder or paste that contains calcium; incubating themixture for a period of time to form covalent bonds between theparticulates; and removing the solid forms from the form works.Alternatively, the compositions may be combined and added together tothe material within the form works or combined with the material priorto addition to the form works.

Another embodiment of the invention is directed to the structure andcomposition of form works. Preferred form works comprises athermoplastic material that can be molded or extruded into a desiredshape. Preferred thermoplastics include, but are not limited to plasticssuch as polypropylene, polystyrene, polyethylene including HDPE (highdensity polyethylene), LPDE and reclaimed LDPE (low densitypolyethylene), and cross-linked polyethylene, glass and most anyformable polymer. Preferably, the polymer material is provided aspellets or lens shapes that range in thickness and uniformity. Thepellets are filled in a porous mold and steamed under pressure (the moldis not under pressure, pressure just from the steam). The resultingproduct provides a designed flow directional material, and changes tothe gradation impact the flow direction, speed and retained saturation.Shapes may be pressed with temporary binder and tops shaded without theneed of formworks.

Preferably the multiple form works comprises 5, 10, 50, 100, 500, 1,000,10,000, 100,000 1,000,000 or more forms at a time. The number of formworks that can be simultaneously treated is limited only by thecomplexity of the mechanics and space available. These form works may bestacked or provided in a single layer or pallet. Formwork may havevertical walls which are connected together forming cavity there betweento receive the aggregate material. Formworks may also have a floor and,alternatively, the bottom of the formwork may be left open if supportedby a porous surface such as soil, or aggregate and composition may bemixed and pressed into molds or extruded. Preferably, vertical walls areat least the inside surfaces thereof, are made of a non-reactive,non-porous material or coating such as cast or extruded acrylic resin.This enables one to easily remove the construction material or the brickfrom the formwork after it has solidified. In addition, the verticalwalls and floor of formwork may have textures to form textures in theresulting brick.

Preferably the colored aggregate material comprises rock, stone, glass,fiberglass, wood, biomass, paper, metal, plastic, polymers, rubber,imitation rubber, vinyl, minerals, recycled material including any ofthe aforementioned materials or combinations thereof, and/or mixingcomprising spraying the composition as a liquid onto the aggregatematerial. Preferably the form works are substantially submerged duringthe incubating and air is bubbled to the submerged form works.Preferably a third composition is added to the mixture repeatedly duringincubating which drains through the bottom panel and, optionally, isrecycled. Preferably, incubating is performed under ambient conditionsand the third composition contains calcium chloride, calcium acetate,calcium phosphate, calcium carbonate, calcium lactate, calcium nitrate,or a calcium salt. Preferably the pH of the mixture is monitored duringthe incubating. Preferably the solid forms are blocks, boards, bricks,pavers, panels, tiles, or veneer, and the mixture further containsfibers or nanofibers that are, for example, fibers or nanofibers ofwood, glass, plastic, metal or a polymer. The solid forms can bepartially or uniformly porous containing a network of holes or gaps.Holes can be of a predetermined size and/or structure such as, forexample, at least 5 microns, at least 10 microns, at least 20 microns,or at least 50 microns in diameter. Alternatively, solid forms can bemanufactured with materials that provide virtually no or few holes. Forexample, adding a non-porous material to the aggregate mixture cancreate complex and extended pathways that render the form impermeable tofluids.

Another embodiment of the invention comprises compositions containingurease producing cells or cell spores that are coated with nutrientmedia and contain a coloring agent or pigment. Preferably the nutrientmedia further contains additional urease producing cells or cell spores,and/or nutrients to promote the proliferation of additional cells thathave been added to the aggregate that are beneficial to the finalproduct. Also preferably the coloring agent or pigment maintain thecells and/or spores in an inactive and/or dormant state fortransportation and/or storage.

Another embodiment of the invention is directed to compositions, methodsand systems for the treatment of artificially colored aggregatematerials comprised of particles with a composition comprising one ormore of a nitrogen source such as for example urea, a calcium source(e.g., calcium ions) and urease or urease producing cells. Preferablyparticles have a diameter (e.g., actual, average or effective diameter)of less than 1 mm and preferably less than 0.5 mm, more preferably lessthan 0.1 mm and more preferably less than 50 μm. Especially preferredparticles sizes include from 10 μm to 1 mm, from 100 μm to 0.5 mm, from200 μm to 1 mm and various combinations thereof. Particles include, forexample, spores, carbon dust, dust or soot from cement or brickmanufacture, cement block manufacture, foundry operations, grindinglimestone, sand tailings, mining, smelters, paint manufacturing andbyproducts of other manufacturing processes such as slag. Particles maybe obtained and collected from available or implemented dust controlprocedures. Particles may be of mixed sizes including but not limited tosizes equal to and greater than preferred sizes, particles equal to andless that preferred sizes, and combinations of preferred sizes andmixtures thereof. Particles that are aggregates and more sizableparticles may include recycled and/or recyclable materials. The nitrogensource of the composition may be a single chemical, such as urea of anygrade and purity and is preferably commercially obtained. Calcium ionsare preferably obtained from commercially available sources such as, forexample, calcium chloride. Urease enzyme or urease-producing bacteriamay be included in the composition. Urease-producing bacteria include,but are not limited to the bacteria Sporosarcina Pasteurii, SporosarcinaUreae, Proteus Vulgaris, Bacillus Sphaericus, Myxococcus Xanthus,Proteus Mirabilis, Helicobacter Pylori and combinations thereof. Ureaseproducing cells includes non-viable cells that contain enzyme such as,for example, mycells, cells composed of lipids or fatty acids, and cellscontaining urease. Urease and/or urease-producing cells may produce orrelease a predetermined amount of enzyme over a defined period of time.Preferably, the amount of urease released per cell is sufficiently rapidto allow for the rapid creation of calcium carbonate in the presence ofnitrogen and calcium ions.

Preferably, the colored particles are combined with a nitrogen source(e.g., urea), urease and/or urease producing cells, calcium ions andpreferably water to create a homogenous slurry. The slurry can bepainted or sprayed onto objects and/or surfaces creating a layer orcrust, molded into forms that solidify into objects which may becomplete or partially solid, or otherwise pooled for immersion ordipping of objects to be coated with the slurry material again creatinglayers or a crust over the object surfaces. Objects may contain one ormore layers as desired, and layers may be permeable or impermeable towater or improve resistant to wear from weather conditions such as sundamage, snow, ice and rain. Slurries that provide increased resistanceare preferably composed with aggregate materials that are particles ofless than 0.1 mm diameter. As the liquid dries, calcium carbonate bondsform between the particles and/or the particles and the object. Theresult can be an object containing an outer shell of hardened calciumcarbonate or a formed structure. Objects that can be manufacturedaccording to the invention and/or layered with a crust or coating of theinvention include, but are not limited to bricks, cement blocks, pavers,counter tops, glass, fiberglass, polymer and acrylic structures, siding,walls, yard art, slate and rock structures, tiles, paving stones, steps,roofing material, gutters, cement walls and planks, patios, balconies,fencing and combinations thereof.

The following examples illustrate embodiments of the invention, butshould not be viewed as limiting the scope of the invention.

EXAMPLES Example 1 Loose Aggregate Study

A loose aggregate sample was collected and was tested for color fastnesswith tap water, dish soap, and 10% sodium hypochlorite (concentratedbleach). Four small samples of the aggregate were placed into a 100 mLsample collection cups and each rinsed with a different type of solutionuntil the liquid ran clear.

Some pigment was removed from the aggregate with all solutions, howeverfor the tap water and dish soap it seemed that only any loose pigmentwas removed, the overall color of the dyed aggregate remained the same.The bleach solution removed more color from the aggregate, whichremained a dark red albeit slightly lighter than the tap water and dishsoap samples. Although bleach would remove some color from theaggregate, tap water and normal dish soap had little effect on colorfastness of loose pigmented aggregate.

Example 2 Biologically Cemented Aggregate and Portland Cement ConcreteComparative Study

Two pigmented biologically cemented units and two pigmented concretethin facing bricks were selected to test color fastness. One of each ofthe units were partially submerged (about 50%) in 10% sodiumhypochlorite and the other units were placed in ALCONOX (all-purposeindustrial detergent) at a concentration of 1 g ALCONOX to 700 mL of tapwater. All of the units were removed from their respective solutionsafter a few hours and scrubbed with a hard bristled brush to attempt toremove as much color as possible. Fresh solutions were made and theunits were placed back into their respective solutions. The units sat inthe solutions for a total of 46 hours for the biologically cemented testunits and 42.5 hours for the concrete units. The biologically cementedtest unit in bleach exhibited very little color change as compared tothe unsubmerged portion of the unit. The concrete units exhibitedremoval of surface coloring by scrubbing with either bleach or ALCONOXto the point where some of the aggregate was visible behind the color.

Overall color fastness of biologically cemented test units was superiorto that of uncemented pigmented aggregate. As compared to the concreteunits, the biologically cemented test units show greater abrasivecolorfastness.

Other embodiments and uses of the invention will be apparent to thoseskilled in the art from consideration of the specification and practiceof the invention disclosed herein. All references cited herein,including all publications, U.S. and foreign patents and patentapplications, are specifically and entirely incorporated by reference.The term comprising, where ever used, is intended to include the termsconsisting and consisting essentially of. Furthermore, the termscomprising, including, and containing are not intended to be limiting.It is intended that the specification and examples be consideredexemplary only with the true scope and spirit of the invention indicatedby the following claims.

1. A pigmented masonry made by the method comprising: combining apigment with particles of an aggregate material to form a mixture,wherein the mixture contains 5% or less of water by weight; agitatingthe mixture to disburse the pigment over surfaces of the particles;adding 1% or less of water by weight and continuing agitating themixture; combining the pigment and the particles with urease enzyme orurease-producing cells or spores, nutrients, a calcium source and anitrogen source to form a composition; incubating the composition atambient temperature for a period of time to form calcium carbonate,whereby the calcium carbonate affixes the pigment to the particles ofaggregate material; and forming the pigmented masonry.
 2. The pigmentedmasonry of claim 1, wherein the pigment does not leach from the masonryupon exposure to environmental conditions for a period of time.
 3. Thepigmented masonry of claim 2, wherein the environmental conditionscomprise one or more of rain, snow, visible light, rain, and temperaturevariations, and the period of time is the useful life of the masonry. 4.The pigmented masonry of claim 2, wherein the period of time comprisesten years or more.
 5. A pigmented masonry made by a method ofmanufacturing a simulated-stone masonry comprising: combining a pigmentwith particles of an aggregate material to form a mixture wherein themixture contains 5% or less of water by weight; agitating the mixture todisburse the pigment over surfaces of the particles; adding 1% of waterto the mixture and continue agitating the mixture; combining thepigmented particles with urease enzyme or urease-producing cells orspores, nutrients, a calcium source and a nitrogen source to form acomposition; adding one or more additional pigments to the surface ofthe composition; incubating the composition for a period of time to formcalcium carbonate; forming the simulated-stone masonry.
 6. The pigmentedmasonry of claim 5, wherein the pigment does not leach from the masonryupon exposure to environmental conditions for a period of time.
 7. Thepigmented masonry of claim 6, wherein the environmental conditionscomprise one or more of rain, snow, visible light, rain, and temperaturevariations, and the period of time is the useful life of the masonry. 8.The pigmented masonry of claim 6, wherein the period of time comprisesten years or more.
 9. A composition containing urease producingmicroorganisms and a pigment.
 10. The composition of claim 9, whereinthe microorganisms comprise one or more of parasites, eukaryotic cells,bacterial cells, algae and spores.
 11. The composition of claim 9wherein the microorganisms are encapsulated, microencapsulated or coatedwith nutrients, proteins, polysaccharides, or polymers.
 12. Thecomposition of claim 9, which is a powder, a paste, a gel or an aqueoussolution.
 13. The composition of claim 9, wherein the pigment comprisespurple, blue, orange, green, yellow, red, brown, black and/or whitepigments.